The present invention relates to a novel process for the preparation of 3-aryl-benzofuran-ones, which are suitable for stabilising organic materials against oxidative, thermal or light-induced degradation.
The best processes hitherto for the preparation of 3-aryl-benzofuranones are described, for example, in U.S. Pat. No. 4,325,863 and U.S. Pat. No. 5,607,624.
The process disclosed in U.S. Pat. No. 4,325,863 (Example 1, column 8, lines 35-45) for the preparation of 3-phenyl-3H-benzofuran-2-ones, for example 5,7-di-tert-butyl-3-phenyl-3H-benzofuran-2-one of formula C, comprises reacting the 2,4-di-tert-butylphenol of formula A with the mandelic acid of formula B, with removal of water. 
A disadvantage of that process is that it requires the use of mandelic acids substituted on the phenyl ring or heterocyclic mandelic acids. Not very many of those mandelic acids are known from the literature, however, and the known synthesis procedures for the preparation thereof are relatively complicated.
The process disclosed in U.S. Pat. No. 5,607,624 (Example 1, column 24) for the preparation of 3-phenyl-3H-benzofuran-2-ones substituted on the 3-phenyl ring, for example 5,7-di-tert-butyl-3-(2,5-dimethyl-phenyl)-3H-benzofuran-2-one of formula F, comprises reacting the 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one of formula D with p-xylene of formula E, with removal of water. 
A disadvantage of that process is that, for the preparation of unsubstituted 3phenyl-benzo-furanone derivatives, it requires the use of benzene, which is carcinogenic, instead of p-xylene.
R. F. Heldeweg, H. Hogeveen, J. Amer. Chem. Soc. 98 (19), 6040-6042 (1976) disclose novel rhodium-catalyzed additions of carbon monoxide to reactive dienes and enones with formation of five-membered rings.
There is therefore still a need to find an efficient process for the preparation of 3aryl-benzofuranones that does not have the disadvantages mentioned above.
The present invention therefore relates to a process for the preparation of compounds of formula I 
wherein, when n is 1,
R1 is naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, xcex2-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, each of which is unsubstituted or substituted by fluorine, hydroxy, C1-C18alkyl, C1-C18alkoxy, C1-C18alkylthio, di-(C1-C4alkyl)amino, phenyl, benzyl, benzoyl or by benzoyloxy or R1 is a radical of formula II or III 
when n is 2,
R1 is phenylene or naphthylene each unsubstituted or substituted by C1-C4alkyl or by fluorine; or is xe2x80x94R6xe2x80x94Xxe2x80x94R7xe2x80x94,
R2, R3, R4 and R5 are each independently of the others hydrogen, fluorine, hydroxy, C1-C25-alkyl, C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted phenyl, unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; C1-C18alkoxy, C1-C18alkylthio, C1-C4alkylamino, di-(C1-C4alkyl)amino, C1-C25alkanoyloxy, C1-C25alkanoylamino; C3-C25alkanoyloxy interrupted by oxygen, sulfur or by 
xe2x80x83C6-C9cycloalkylcarbonyloxy, benzoyloxy or C1-C12alkyl-substituted benzoyloxy, or furthermore the radicals R2 and R3 or the radicals R3 and R4 or the radicals R4 and R5, together with the carbon atoms to which they are bonded, form a benzo ring, R4 is additionally xe2x80x94(CH2)pxe2x80x94COR9 or xe2x80x94(CH2)qOH or, when R3 and R5 are hydrogen, R4 is additionally a radical of formula IV 
wherein R1 is as defined above for the case where n=1,
R6 and R7 are each independently of the other phenylene or naphthylene each unsubstituted or substituted by C1-C4alkyl,
R8 is C1-C8alkyl,
R9 is hydroxy,       [                  xe2x80x94O        -            ⁢              1        r            ⁢              M                  r          +                      ]    ,
xe2x80x83C1-C18alkoxy or 
R10 and R11 are each independently of the other hydrogen, CF3, C1-C12alkyl or phenyl, or R10 and R11, together with the carbon atom to which they are bonded, form a C5-C8cycloalkylidene ring unsubstituted or substituted by from 1 to 3 C1-C4alkyl groups;
R12 and R13 are each independently of the other hydrogen or C1-C18alkyl,
R14 is hydrogen or C1-C18alkyl,
R19, R20, R21, R22 and R23 are each independently of the others hydrogen, fluorine, hydroxy, C1-C25alkyl; C2-C25alkyl interrupted by oxygen, sulfur or by 
xe2x80x83C1-C25alkoxy; C2-C25alkoxy interrupted by oxygen, sulfur or by 
xe2x80x83C1-C25alkylthio, C7-C9phenylalkyl, C7-C9phenylalkoxy, unsubstituted or C1-C4alkyl-substituted phenyl; unsubstituted or C1-C4alkyl-substituted phenoxy; unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkoxy; di(C1-C4alkyl)amino, C1-C25-alkanoyl; C3-C25alkanoyl interrupted by oxygen, sulfur or by 
xe2x80x83C1-C25alkanoyloxy; C3-C25alkanoyloxy interrupted by oxygen, sulfur or by 
xe2x80x83C1-C25alkanoylamino, C6-C9cycloalkylcarbonyl, C6-C9cycloalkylcarbonyloxy, benzoyl or C1-C12alkyl-substituted benzoyl; benzoyloxy or C1-C12alkyl-substituted benzoyloxy; 
R24 is hydrogen, C1-C4alkyl, or unsubstituted or C1-C4alkyl-substituted phenyl,
R25 and R26 are hydrogen, C1-C4alkyl or phenyl, with the proviso that at least one of the radicals R25 and R26 is hydrogen,
R27 and R28 are each independently of the other hydrogen, C1-C4alkyl or phenyl,
R29 is hydrogen or C1-C4alkyl,
R30 is hydrogen, unsubstituted or C1-C4alkyl-substituted phenyl; C1-C25alkyl; C2-C25alkyl interrupted by oxygen, sulfur or by 
xe2x80x83C7-C9phenylalkyl unsubstituted or substituted on the phenyl radical by from 1 to 3 C1-C4alkyl groups; or C7-C25phenylalkyl interrupted by oxygen, sulfur or by 
xe2x80x83and unsubstituted or substituted on the phenyl radical by from 1 to 3 C1-C4alkyl groups,
R31 is hydrogen or C1-C4alkyl,
R32 is hydrogen, C1-C25alkanoyl; C3-C25alkanoyl interrupted by oxygen, sulfur or by 
xe2x80x83C2-C25alkanoyl substituted by a di(C1-C6alkyl) phosphonate group; C6-C9cyclo-alkylcarbonyl, thenoyl, furoyl, benzoyl or C1-C12alkyl-substituted benzoyl; 
R33 is hydrogen or C1-C8alkyl,
R34 is a direct bond, C1-C18alkylene; C2-C18alkylene interrupted by oxygen, sulfur or by 
xe2x80x83C2-C20alkylidene, C7-C20phenylalkylidene, C5-C8cycloalkylene, C7-C8bicyclo-alkylene, unsubstituted or C1-C4alkyl-substituted phenylene, 
R35 is hydroxy,       [                  xe2x80x94O        -            ⁢              1        r            ⁢              M                  r          +                      ]    ,
xe2x80x83C1-C18alkoxy or 
R36 is oxygen, xe2x80x94NHxe2x80x94 or 
R37 is C1-C18alkyl or phenyl,
M is an r-valent metal cation,
X is a direct bond, oxygen, sulfur or xe2x80x94NR14xe2x80x94,
n is 1 or 2,
p is 0, 1 or 2,
q is 1, 2, 3, 4, 5 or 6,
r is 1, 2 or 3, and
s is 0, 1 or 2,
which process comprises reacting a compound of formula V 
xe2x80x83wherein
xe2x80x83R1 and n are as defined above,
xe2x80x83R2, R3, Rxe2x80x24 and R5 are each independently of the others hydrogen, fluorine, hydroxy, C1-C25alkyl, C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted phenyl, unsubstituted or C1-C4alkyl-substituted C5-C8-cycloalkyl; C1-C18alkoxy, C1-C18alkylthio, C1-C4alkylamino, di(C1-C4alkyl)amino, C1-C25alkanoyloxy, C1-C25alkanoylamino; C3-C25alkanoyloxy interrupted by oxygen, sulfur or by 
xe2x80x83C6-C9cycloalkylcarbonyloxy, benzoyloxy or C1-C12alkyl-substituted benzoyloxy, or furthermore the radicals R2 and R3 or the radicals R3 and Rxe2x80x24 or the radicals Rxe2x80x24 and R5, together with the carbon atoms to which they are bonded, form a benzo ring, Rxe2x80x24 is additionally xe2x80x94(CH2)pxe2x80x94COR9 or xe2x80x94(CH2)qOH or, when R3 and R5 are hydrogen,
xe2x80x83Rxe2x80x24 is additionally a radical of formula VI 
xe2x80x83wherein R1 is as defined above for the case where n=1,
xe2x80x83with carbon monoxide in the presence of a catalyst.
Alkanoyl having up to 25 carbon atoms is a branched or unbranched radical, for example formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, icosanoyl or docosanoyl. Alkanoyl has preferably from 2 to 18, especially from 2 to 12, e.g. from 2 to 6, carbon atoms. Special preference is given to acetyl.
C2-C25Alkanoyl substituted by a di(C1-C6alkyl) phosphonate group is, for example, (CH3CH2O)2POCH2COxe2x80x94, (CH3O)2POCH2COxe2x80x94, (CH3CH2CH2CH2O)2POCH2COxe2x80x94, (CH3CH2O)2POCH2CH2COxe2x80x94, (CH3O)2POCH2CH2COxe2x80x94, (CH3CH2CH2CH2O)2POCH2CH2COxe2x80x94, (CH3CH2O)2PO(CH2)4COxe2x80x94, (CH3CH2O)2PO(CH2)8COxe2x80x94 or (CH3CH2O)2PO(CH2)17COxe2x80x94.
Alkanoyloxy having up to 25 carbon atoms is a branched or unbranched radical, for example formyloxy, acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy, tetradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy, octadecanoyloxy, icosanoyloxy or docosanoyloxy. Preference is given to alkanoyloxy having from 2 to 18, especially from 2 to 12, e.g. from 2 to 6, carbon atoms. Special preference is given to acetoxy.
C3-C25Alkenoyloxy interrupted by oxygen, sulfur or by 
is, for example, CH3OCH2CH2CHxe2x95x90CHCOOxe2x80x94 or CH3OCH2CH2OCHxe2x95x90CHCOOxe2x80x94.
C3-C25Alkanoyl interrupted by oxygen, sulfur or by 
is, for example, CH3xe2x80x94Oxe2x80x94CH2COxe2x80x94, CH3xe2x80x94Sxe2x80x94CH2COxe2x80x94, CH3xe2x80x94N(CH3)xe2x80x94CH2COxe2x80x94, CH3xe2x80x94Oxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2COxe2x80x94, CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)2Oxe2x80x94CH2COxe2x80x94, CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)3xe2x80x94Oxe2x80x94CH2COxe2x80x94 or CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)4xe2x80x94CH2COxe2x80x94.
C3-C25Alkanoyloxy interrupted by oxygen, sulfur or by 
is, for example, CH3xe2x80x94Oxe2x80x94CH2COOxe2x80x94, CH3xe2x80x94Sxe2x80x94CH2COOxe2x80x94, CH3xe2x80x94N(CH3)xe2x80x94CH2COOxe2x80x94, CH3xe2x80x94Oxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2COOxe2x80x94, CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)2Oxe2x80x94CH2COOxe2x80x94, CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)3Oxe2x80x94CH2COOxe2x80x94 or CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)4Oxe2x80x94CH2COOxe2x80x94.
C6-C9Cycloalkylcarbonyl is, for example, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl or cyclooctylcarbonyl. Preference is given to cyclohexylcarbonyl.
C6-C9Cycloalkylcarbonyloxy is, for example, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy or cyclooctylcarbonyloxy. Preference is given to cyclohexylcarbonyloxy.
C1-C12Alkyl-substituted benzoyl, which carries preferably from 1 to 3, especially 1 or 2, alkyl groups, is, for example, o-, m- or p-methylbenzoyl, 2,3-dimethylbenzoyl, 2,4-dimethylbenzoyl, 2,5-dimethylbenzoyl, 2,6-dimethylbenzoyl, 3,4-dimethylbenzoyl, 3,5-dimethylbenzoyl, 2-methyl-6-ethylbenzoyl, 4-tert-butylbenzoyl, 2-ethylbenzoyl, 2,4,6-trimethylbenzoyl, 2,6-dimethyl-4-tert-butylbenzoyl or 3,5-di-tert-butylbenzoyl. Preferred substituents are C1-C8-alkyl, especially C1-C4alkyl.
C1-C12Alkyl-substituted benzoyloxy, which carries preferably from 1 to 3, especially 1 or 2, alkyl groups, is, for example, o-, m- or p-methylbenzoyloxy, 2,3-dimethylbenzoyloxy, 2,4-dimethylbenzoyloxy, 2,5-dimethylbenzoyloxy, 2,6-dimethylbenzoyloxy, 3,4-dimethylbenzoyloxy, 3,5-dimethylbenzoyloxy, 2-methyl-6-ethylbenzoyloxy, 4-tert-butylbenzoyloxy, 2-ethylbenzoyloxy, 2,4,6-trimethylbenzoyloxy, 2,6-dimethyl-4-tert-butylbenzoyloxy or 3,5-di-tert-butylbenzoyloxy. Preferred substituents are C1-C8alkyl, especially C1-C4alkyl.
Alkyl having up to 25 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl or docosyl. One of the preferred definitions for R2 and R4 is, for example, C1-C18alkyl. An especially preferred definition for R4 is C1-C4alkyl.
C2-C25Alkyl interrupted by oxygen, sulfur or by 
is, for example, CH3xe2x80x94Oxe2x80x94CH2xe2x80x94, CH3xe2x80x94Sxe2x80x94CH2xe2x80x94, CH3xe2x80x94N(CH3)xe2x80x94CH2xe2x80x94, CH3xe2x80x94Oxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2xe2x80x94, CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)2Oxe2x80x94CH2xe2x80x94, CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)3Oxe2x80x94CH2xe2x80x94 or CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)4Oxe2x80x94CH2xe2x80x94.
C7-C9Phenylalkyl is, for example, benzyl, xcex1-methylbenzyl, xcex1,xcex1-dimethylbenzyl or 2-phenylethyl. Preference is given to benzyl and xcex1,xcex1-dimethylbenzyl.
C7-C9Phenylalkyl unsubstituted or substituted on the phenyl radical by from 1 to 3 C1-C4alkyl groups is, for example, benzyl, xcex1-methylbenzyl, xcex1,xcex1-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-tertbutylbenzyl. Preference is given to benzyl.
C7-C25Phenylalkyl interrupted by oxygen, sulfur or by 
and unsubstituted or substituted on the phenyl radical by from 1 to 3 C1-C4alKyl groups is a branched or unbranched radical, for example phenoxymethyl, 2-methyl-phenoxymethyl, 3-methyl-phenoxymethyl, 4-methyl-phenoxymethyl, 2,4-dimethyl-phenoxymethyl, 2,3-dimethyl-phenoxymethyl, phenyl-thiomethyl, N-methyl-N-phenyl-aminomethyl, N-ethyl-N-phenyl-aminomethyl, 4-tert-butyl-phenoxymethyl, 4-tert-butyl-phenoxyethoxy-methyl, 2,4-di-tert-butyl-phenoxymethyl, 2,4-di-tert-butyl-phenoxyethoxymethyl, phenoxyethoxyethoxyethoxymethyl, benzyloxymethyl, benzyloxyethoxymethyl, N-benzyl-N-ethyl-aminomethyl or N-benzyl-N-isopropyl-aminomethyl.
C7-C9Phenylalkoxy is, for example, benzyloxy, xcex1-methylbenzyloxy, xcex1,xcex1-dimethylbenzyloxy or 2-phenylethoxy. Preference is given to benzyloxy.
C1-C4Alkyl-substituted phenyl, which contains preferably from 1 to 3, especially 1 or 2, alkyl groups, is, for example, o-, m- or p-methylphenyl, 2,3-dimethyiphenyi, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.
C1-C4Alkyl-substituted phenoxy, which contains preferably from 1 to 3, especially 1 or 2, alkyl groups, is, for example, o-, m- or p-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy or 2,6-diethylphenoxy.
Unsubstituted or C1-C4alkyl-substituted C5-Cacycloalkyl is, for example, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Preference is given to cyclohexyl and tert-butylcyclohexyl.
Unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkoxy is, for example, cyclopentyloxy, methylcyclopentyloxy, dimethylcyclopentyloxy, cyclohexyloxy, methylcyclohexyloxy, dimethylcyclohexyloxy, trimethylcyclohexyloxy, tert-butylcyclohexyloxy, cycloheptyloxy or cyclooctyloxy. Preference is given to cyclohexyloxy and tert-butylcyclohexyloxy.
Alkoxy having up to 25 carbon atoms is a branched or unbranched radical, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Preference is given to alkoxy having from 1 to 12, especially from 1 to 8, e.g. from 1 to 6, carbon atoms.
C2-C25Alkoxy interrupted by oxygen, sulfur or by 
is for example, CH3xe2x80x94Oxe2x80x94CH2CH2Oxe2x80x94, CH3xe2x80x94Sxe2x80x94CH2CH2Oxe2x80x94, CH3xe2x80x94N(CH3)xe2x80x94CH2CH2Oxe2x80x94, CH3xe2x80x94Oxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2CH2O xe2x80x94, CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)2Oxe2x80x94CH2CH2Oxe2x80x94, CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)3Oxe2x80x94CH2CH2Oxe2x80x94 or CH3xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)4Oxe2x80x94CH2CH2Oxe2x80x94.
Alkylthio having up to 25 carbon atoms is a branched or unbranched radical, for example methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, pentylthio, isopentylthio, hexylthio, heptyithio, octylthio, decylthio, tetradecylthio, hexadecylthio or octadecylthio. Preference is given to alkyithio having from 1 to 12, especially from 1 to 8, e.g. from 1 to 6, carbon atoms.
Alkylamino having up to 4 carbon atoms is a branched or unbranched radical, for example methylamino, ethylamino, propylamino, isopropylamino, n-butylamino, isobutylamino or tert-butylamino.
Di(C1-C4alkyl)amino means also that the two radicals are each independently of the other branched or unbranched, for example, dimethylamino, methylethylamino, diethylamino, methyl-n-propylamino, methylisopropylamino, methyl-n-butylamino, methylisobutylamino, ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino, ethyl-tert-butylamino, diethylamino, diisopropylamino, isopropyl-n-butylamino, isopropylisobutylamino, di-n-butylamino or di-isobutylamino.
Alkanoylamino having up to 25 carbon atoms is a branched or unbranched radical, for example formylamino, acetylamino, propionylamino, butanoylamino, pentanoylamino, hexanoylamino, heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undecanoylamino, dodecanoylamino, tridecanoylamino, tetradecanoylamino, pentadecanoylamino, hexadecanoylamino, heptadecanoylamino, octadecanoylamino, icosanoylamino or docosanoylamino. Preference is given to alkanoylamino having from 2 to 18, especially from 2 to 12, e.g. from 2 to 6, carbon atoms.
C1-C18Alkylene is a branched or unbranched radical, for example methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene. Preference is given to C1-C12alkylene, especially C1-C8alkylene. An especially preferred definition for R56 is C2-C8alkylene, especially C4-C8alkylene, for example tetramethylene or pentamethylene.
C2-C18Alkylene interrupted by oxygen, sulfur or by 
is, for example, xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94Sxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94N(CH3)xe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94Oxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)2Oxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)3Oxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94(Oxe2x80x94CH2CH2xe2x80x94)4Oxe2x80x94CH2xe2x80x94 or xe2x80x94CH2CH2xe2x80x94Sxe2x80x94CH2CH2xe2x80x94.
Alkylidene having from 2 to 20 carbon atoms is, for example, ethylidene, propylidene, butylidene, pentylidene, 4-methylpentylidene, heptylidene, nonylidene, tridecylidene, nonadecylidene, 1-methylethylidene, 1-ethylpropylidene or 1-ethylpentylidene. Preference is given to C2-C8alkylidene.
Phenylalkylidene having from 7 to 20 carbon atoms is, for example, benzylidene, 2-phenylethylidene or 1-phenyl-2-hexylidene. Preference is given to C7-C9phenylalkylidene.
C5-C8Cycloalkylene is a saturated hydrocarbon group having two free valences and at least one ring unit and is, for example, cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene. Preference is given to cyclohexylene.
C7-C8Bicycloalkylene is, for example, bicycloheptylene or bicyclooctylene.
Phenytene or naphthylene each unsubstituted or substituted by C1-C4alkyl is, for example, 1,2-, 1,3- or 1,4-phenylene or 1,2-, 1,3-, 1,4-, 1,6-, 1,7-, 2,6- or 2,7-naphthylen is given to 1,4-phenylene.
A C5-C8cycloalkylidene ring substituted by C1-C4alkyl, which contains preferably from 1 to 3, especially 1 or 2, branched or unbranched alkyl group radicals, is, for example, cyclopentylidene, methylcyclopentylidene, dimethylcyciopentylidene, cyclohexylidene, methylcyclohexylidene, dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene or cyclooctylidene. Preference is given to cyclohexylidene and tert-butylcyclohexylidene.
A mono-, di- or tri-valent metal cation is preferably an alkali metal cation, alkaline earth metal cation or aluminium cation, for example Na+, K+, Mg++, Ca++ or Al+++.
Dendrimeric, oligomeric or polymeric C4-C100hydrocarbon radicals are, for example, those such as are disclosed by R. Mxc3xclhaupt et al. in Angew. Chem., Int. Ed. 32 (9), 1306 (1993).
Of interest is a process for the preparation of compounds of formula I wherein,
when n is 2,
R1 is phenylene or xe2x80x94R6xe2x80x94Xxe2x80x94R7xe2x80x94,
R6 and R7 are phenylene, xe2x80x94X is oxygen or xe2x80x94NR14xe2x80x94, and
R14 is C1-C4alkyl.
Likewise of interest is a process for the preparation of compounds of formula I wherein R19, R20, R21, R22 and R23 are each independently of the others hydrogen, fluorine, hydroxy, C1-C18alkyl; C2-C18alkyl interrupted by oxygen or by sulfur; C1-C18alkoxy; C2-C18alkoxy interrupted by oxygen or by sulfur; C1-C18alkylthio, C7-C9phenylalkyl, C7-C9phenylalkoxy, unsubstituted or C1-C4alkyl-substituted phenyl; phenoxy, cyclohexyl, C5-C8cycloalkoxy, di(C1-C4-alkyl)amino, C1-C12alkanoyl; C3-C12alkanoyl interrupted by oxygen or by sulfur; C1-C12-alkanoyloxy; C3-C12alkanoyloxy interrupted by oxygen or by sulfur; C1-C12alkanoylamino, cyclohexylcarbonyl, cyclohexylcarbonyloxy, benzoyl or C1-C4alkyl-substituted benzoyl; benzoyloxy or C1-C4alkyl-substituted benzoyloxy; 
R24 is hydrogen or C1-C4alkyl,
R25 and R26 are hydrogen or C1-C4alkyl, with the proviso that at least one of the radicals R25 and R26 is hydrogen,
R27 and R28 are each independently of the other hydrogen or C1-C4alkyl,
R29 is hydrogen,
R30 is hydrogen, phenyl, C1-C18alkyl; C2-C18alkyl interrupted by oxygen or by sulfur; C7-C9-phenylalkyl; or C7-C18phenylalkyl interrupted by oxygen or by sulfur and unsubstituted or substituted on the phenyl radical by from 1 to 3 C1-C4alkyl groups,
R31 is hydrogen or C1-C4alkyl,
R32 is hydrogen, C1-C18alkanoyl; C3-C12alkanoyl interrupted by oxygen or by sulfur; C2-C12-alkanoyl substituted by a di(C1-C6alkyl) phosphonate group; C6-C9cycloalkylcarbonyl, benzoyl, 
R33 is hydrogen or C1-C4alkyl,
R34 is C1-C12alkylene, C2-C8alkylidene, C7-C12phenylalkylidene, C5-C8cycloalkylene or phenylene,
R35 is hydroxy,       [                  xe2x80x94O        -            ⁢              1        r            ⁢              M                  r          +                      ]    ,
xe2x80x83or C1-C18alkoxy,
R36 is oxygen or xe2x80x94NHxe2x80x94,
R37 is C1-C8alkyl or phenyl, and
s is 1 or 2.
Of special interest is a process for the preparation of compounds of formula I wherein, when n is 1,
R1 is phenanthryl, thienyl, dibenzofuryl, unsubstituted or C1-C4alkyl-substituted carbazolyl; or fluorenyl, or R1 is a radical of formula II 
wherein
R19, R20, R21, R22 and R23 are each independently of the others hydrogen, fluorine, hydroxy, C1-C18alkyl, C1-C18alkoxy, C1-C18alkylthio, phenyl, benzoyl, benzoyloxy or 
R29 is hydrogen,
R30 is hydrogen, phenyl or C1-C18alkyl,
R31 is hydrogen or C1-C4alkyl, and
R32 is hydrogen, C1-C12alkanoyl or benzoyl.
Likewise of special interest is a process for the preparation of compounds of formula I wherein
R19 is hydrogen or C1-C4alkyl,
R20 is hydrogen or C1-C4alkyl,
R21 is hydrogen, fluorine, hydroxy, C1-C12alkyl, C1-C4alkoxy, C1-C4alkylthio, phenyl or xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94R32,
R22 is hydrogen or C1-C4alkyl,
R23 is hydrogen or C1-C4alkyl, and
R32 is C1-C4alkanoyl.
Of special interest is, more especially, a process for the preparation of compounds of formula I wherein
R2, R3, R4 and R5 are each independently of the others hydrogen, fluorine, hydroxy, C1-C25alkyl, C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted phenyl; unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; C1-C12alkoxy, C1-C12alkylthio, C1-C4alkylamino, di-(C1-C4alkyl)amino, C1-C18alkanoyloxy, C1-C18alkanoylamino; C3-C18alkanoyloxy interrupted by oxygen, sulfur or by 
C6-C9cycloalkylcarbonyloxy, benzoyloxy or C1-C8alkyl-substituted benzoyloxy, or furthermore the radicals R2 and R3 or the radicals R3 and R4 or the radicals R4 and R5, together with the carbon atoms to which they are bonded, form a benzo ring, R4 is additionally xe2x80x94(CH2)pxe2x80x94COR9 or xe2x80x94(CH2)qOH or, when R3 and R5 are hydrogen, R4 is additionally a radical of formula IV 
R8 is C1-C6alkyl,
R9 is hydroxy, C1-C18alkoxy or 
xe2x80x83R10 and R11 are methyl groups or, together with the carbon atom to which they are bonded, form a C5-C8cycloalkylidene ring unsubstituted or substituted by from 1 to 3 C1-C4alkyl groups;
R12 and R13 are each independently of the other hydrogen or C1-C8alkyl, and
is 2,3,4,5 or 6.
Special preference is given to a process for the preparation of compounds of formula I wherein at least two of the radicals R2, R3, R4 and R5 are hydrogen.
Also very especially preferred is a process for the preparation of compounds of formula I wherein R3 and R5 are hydrogen.
Very special preference is given to a process for the preparation of compounds of formula I wherein
R2, R3, R4 and R5 are each independently of the others hydrogen, fluorine, hydroxy, C1-C18alkyl, C7-C9phenylalkyl, phenyl, C5-C8cycloalkyl, C1-C6alkoxy, cyclohexylcarbonyloxy or benzoyloxy, or furthermore the radicals R2 and R3 or the radicals R3 and R4 or the radicals R4 and R5, together with the carbon atoms to which they are bonded, form a benzo ring, R4 is additionally xe2x80x94(CH2)pxe2x80x94COR9, or, when R3 and R5 are hydrogen, R4 is additionally a radical of formula IV,
R9 is hydroxy or C1-C18alkoxy, and
R10 and R11 are methyl groups or, together with the carbon atom to which they are bonded, form a C5-C8cycloalkylidene ring.
Of preferential interest is a process for the preparation of compounds of formula I wherein
R2 is C1-C18alkyl or cyclohexyl,
R3 is hydrogen,
R4 is C1-C4alkyl, cyclohexyl, xe2x80x94(CH2)pxe2x80x94COR9 or a radical of formula IV,
R5 is hydrogen,
R9 is C1-C4alkyl,
R10 and R11, together with the carbon atom to which they are bonded, form a cyclohexylidene ring, and
p is 2.
Likewise of preferential interest is a process for the preparation of compounds of formula I wherein
R2 is C1-C8alkyl or cyclohexyl,
R3 is hydrogen,
Rxe2x80x24 is C1-C4alkyl, cyclohexyl, xe2x80x94(CH2)pxe2x80x94COR9 or a radical of formula VI,
R5 is hydrogen,
R9 is C1-C4alkyl,
R10 and R11, together with the carbon atom to which they are bonded, form a cyclohexylidene ring, and
p is 2.
Some of the monomeric compounds of formula V are present in the form of dimers of formula Va. 
This equilibrium is temperature-dependent. The dimeric compound of formula Va may also be referred to as a Diels-Alder adduct. The dimeric compounds of formula Va can, together with further compounds of formula V, form trimeric, tetrameric or oligomeric compounds.
For the process according to the invention there may be used both the pure monomeric compound of formula V and the pure dimeric compound of formula Va, a mixture of the two compounds of formula V and Va or a mixture of any possible monomeric, dimeric, trimeric or oligomeric compounds derived from the compound of formula V. Under the reaction conditions, the dimeric, trimeric or oligomeric compounds derived from the compound of formula V form again the monomeric compound of formula V, which reacts with carbon monoxide and shifts the equilibrium towards the monomeric side.
Preferred reaction conditions for the process according to the invention are as follows:
The reaction may be carried out at an elevated temperature, especially at temperatures of from 50 to 200xc2x0 C., in the melt or in a solvent, optionally under slight pressure.
Special preference is given to carrying out the reaction using a large molar excess of carbon monoxide. Special preference is therefore given to a process for the preparation of compounds of formula I wherein the ratio of molar quantities of the compound of formula V to carbon monoxide is from 1:1 to 1:5000.
Preference is given to using, as solvent, pressurised carbon monoxide, which at the same time constitutes the reactant.
As solvents there may, however, also be used solvents that do not participate in the reaction, for example hydrocarbons, ethers and aromatic compounds.
Preferred hydrocarbons are, for example, octane and commercially available isomeric fractions, for example hexane traction, petroleum ether and ligroin.
Preferred ethers are, for example, dibutyl ether, methyl tert-butyl ether and diethylene glycol dimethyl ether.
Examples of aromatic compounds are toluene and xylene.
A preferred catalyst for the process for the preparation of compounds of formula I is a metal catalyst, especially a metal catalyst that is capable of forming a complex with carbon monoxide, for example a transition metal catalyst.
Of preferential interest is a process for the preparation of compounds of formula I wherein the transition metal catalyst is a titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum or copper catalyst. Of special interest is a titanium, vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel or palladium catalyst.
Especially preferred catalysts are, for example, V(CO)6; Cr(CO)6; Mn(CO)6; Mn2(CO)10; Mn(CO)5Br; Fe(CO)5; Fe2(CO)9; Fe3(CO)12; Na2Fe(CO)4; [(cyclopentadienyl)Fe(CO)2 ]2; Co2(CO)8; Co4(CO)12; NaCo(CO)4; Ni(CO)4; Ni(CN)2; NiPRxe2x80x23Xxe2x80x22 wherein Rxe2x80x2 is unsubstituted substituted phenyl, cyclohexyl or isopropyl and Xxe2x80x2 is chlorine or bromine; Ni(PPh3)2(CO)2; Pd(PPh3)4; Pd(PRxe2x80x23)2Xxe2x80x32 wherein Rxe2x80x2 is as defined above and Xxe2x80x3 is chlorine, bromine or iodine; Pd(PPh2Me)2Cl2; Pd(AsPh3)2Cl2; Pd(Br)(Ph)(PPh3)2; Pd(dipp)2 wherein dipp is 1,3-bis(diiso-propylphosphino)propane; PdCl2(Rxe2x80x3CN)2 wherein Rxe2x80x3 is alkyl or phenyl; Pd(acetate)2+PRxe2x80x23 wherein Rxe2x80x2 is as defined above; Rxe2x80x22PCH2CH2CH2PRxe2x80x22 wherein Rxe2x80x2 is as defined above; Pd2(di-benzylidene acetone)3+PRxe2x80x23 wherein Rxe2x80x2 is as defined above; Li2PdCl4; PdCl2+MgCl2; PdCl2+CuCl2; HPtCl6; [PtCl2(SnCl3)2]2xe2x88x92; [Pt(SnCl3)5]3xe2x88x92; Pt(PPh3)2(CO)2; Mo(CO)6; Tc2(CO)10; Ru(CO)5; Ru3(CO)12; RuCl3; Rh2(CO)8; Rh4(CO)12; Rh6(CO)16; [Rh(CO)2Cl]2; [Rh(cyclooctadiene)Cl]2; Rh2(acetate)4; Rh(PPh3)2Cl; W(CO)6; Re2(CO)10; OS(CO)5; Os2(CO)9; OS3(CO)12; Ir2(CO)8 and Ir4(CO)12.
A very especially preferred catalyst is, for example, tetrakis(triphenylphosphine)palladium(0).
Advantageously, the catalyst is used in an amount of from 0.01 to 20% by weight, especially from 0.1 to 10% by weight, e.g. from 0.1 to 5% by weight, based on the weight of the compound of formula V used.
The reaction can also be accelerated by addition of a catalytic amount of a protonic acid or Lewis acid.
Suitable protonic acids are, for example, acids of inorganic or organic salts, for example hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesultonic acid or carboxylic acids, for example formic acid, acetic acid and trifluoroacetic acid. Special preference is given to formic acid and trifluoroacetic acid.
Suitable Lewis acids are, for example, tin tetrachloride, aluminium chloride, zinc chloride, boron trifluoride etherate or anhydrides, for example carboxylic acid anhydrides, especially acetic anhydride. Special preference is given to tin tetrachloride, aluminium chloride and acetic anhydride.
The starting compounds of formula V are, in some instances, known or can be prepared in analogy to the method described by L. Jurd in J. Heterocyclic Chem. 25, 89-96 (1988).
A preferred process for the preparation of the starting compounds of formula V 
wherein the general symbols are as defined above, comprises converting a compound of formula VII 
wherein R1 and n are as defined above,
R2, R3, Rxe2x80x34 and R5 are each independently of the others hydrogen, fluorine, hydroxy, C1-C25alkyl, C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted phenyl, unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; C1-C18alkoxy, C1-C18alkylthio, C1-C4alkylamino, di(C1-C4alkyl)amino, C1C25alkanoyloxy, C1-C25alkanoylamino; C3-C25alkanoyloxy interrupted by oxygen, sulfur or by 
C6-C9cycloalkylcarbonyloxy, benzoyloxy or C1-C12alkyl-substituted benzoyloxy, or furthermore the radicals R2 and R3 or the radicals R3 and Rxe2x80x34 or the radicals Rxe2x80x34 and R5, together with the carbon atoms to which they are bonded, form a benzo ring, Rxe2x80x34 is additionally xe2x80x94(CH2)pxe2x80x94COR9 or xe2x80x94(CH2)qOH or, when R3 and R5 are hydrogen, Rxe2x80x34 is additionally a radical of formula VIII 
wherein R1 is as defined above for the case where n=1, R2, R10 and R11 are as defined above,
R50 is xe2x80x94OR51, xe2x80x94SR52, 
xe2x80x83R51 is C1-C25alkyl; C2-C25alkyl interrupted by oxygen or by sulfur; C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; unsubstituted or C1-C4alkyl-substituted phenyl,
R52 is C1-C25alkyl; C2-C25alkyl interrupted by oxygen or by sulfur; C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; unsubstituted or C1-C4alkyl-substituted phenyl,
R53 and R54 are each independently of the other hydrogen, C1-C25alkyl; C2-C25alkyl interrupted by oxygen or by sulfur; C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; or a dendrimeric, oligomeric or polymeric C4-C100hydrocarbon radical,
R55 is C1-C25alkyl; C2-C25alkyl interrupted by oxygen or by sulfur; C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; unsubstituted or C1-C4alkyl-substituted phenyl; or a radical of formula IX 
wherein R1, R2, R3, Rxe2x80x34, R5 and n are as defined above,
R56 is unsubstituted or C1-C4alkyl-substituted C2-C12alkylene, thermally or using light.
In that conversion the radical HR50 is removed.
The reaction may be carried out at an elevated temperature, especially at temperatures of from 60 to 180xc2x0 C., in the melt or in a solvent.
The reaction may be carried out in the melt or in a solvent, optionally under slight pressure.
As solvents there may be used solvents that do not participate in the reaction, for example hydrocarbons, ethers and aromatic compounds.
Preferred hydrocarbons are, for example, octane and commercially available isomeric fractions, for example hexane fraction, petroleum ether and ligroin.
Preferred ethers are, for example, dibutyl ether, methyl tert-butyl ether and diethylene glycol dimethyl ether.
Examples of aromatic compounds are toluene and xylene.
The reaction can also be accelerated by addition of a catalytic to excess amount of a protonic acid.
Suitable protonic acids are, for example, acids of inorganic or organic salts, for example hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid or carboxylic acids, for example acetic acid and trifluoroacetic acid. Special preference is given to trifluoroacetic acid.
Preference is given to the process for the preparation of compounds of formula V wherein
R50 is xe2x80x94OR51, xe2x80x94SR52, 
xe2x80x83R51 is C1-C12alkyl; C2-C2alkyl interrupted by oxygen; benzyl, C5-C8cycloalkyl or phenyl,
R52 is C1-C12alkyl; C2-C12alkyl interrupted by oxygen; benzyl, C5-C8cycloalkyl or phenyl,
R53 and R54 are each independently of the other hydrogen, C1-C12alkyl; C2-C12alkyl interrupted by oxygen; benzyl, C5-C8cycloalkyl, or a dendrimeric or oligomeric or polymeric C4-C50hydrocarbon radical,
R55 is C1-C12alkyl; C2-C12alkyl interrupted by oxygen; benzyl, C5‥C8cycloalkyl, phenyl or a radical of formula IX 
wherein R1, R2, R3, Rxe2x80x34, R5 and n are as defined above, and
R56 is C2-C8alkylene.
Special preference is given to the process for the preparation of compounds of formula V wherein 
R53 and R54 are each independently of the other hydrogen, C1-C12alkyl, benzyl, cyclohexyl or a dendrimeric C4-C30hydrocarbon radical,
R55 is C1-C12alkyl, benzyl, cyclohexyl, phenyl or a radical of formula IX 
wherein R1, R2, R3, Rxe2x80x34, R5 and n are as defined above, and
R56 is C4-C8alkylene.
Of special interest is the process for the preparation of compounds of formula V wherein 
R53 and R54 are each independently of the other C1-C12alkyl, benzyl or a dendrimeric C4-C30hydrocarbon radical, and
R56 is C4-C6alkylene.
Special preference is given to the process for the preparation of compounds of formula V wherein the conversion to the compound of formula V is carried out in the presence of an acid, especially a carboxylic acid, for example acetic acid and trifluoroacetic acid.
The compounds of formula VII are known or can be obtained by methods known per se, such as those disclosed in Examples 1a, 2a and 3a.
The compounds of formula I can also be prepared in a so-called one-pot process, starting from the compounds of formula VII. In that process, the compounds of formula V are prepared in situ and, without being isolated, are reacted further with carbon monoxide in the presence of a catalyst.
The present invention therefore relates also to a process for the preparation of compounds of formula I 
wherein the general symbols are as defined above, which process comprises converting a compound of formula VII 
wherein the general symbols are as defined above, thermally or using light, to form a compound of formula V 
wherein the general symbols are as defined above, and then, without its being isolated, reacting that compound with carbon monoxide in the presence of a catalyst.
The definitions of the general symbols for the one-pot process according to the invention are the same as for the other process of the invention discussed hereinbefore.
The preferred reaction parameters for the one-pot process correspond to the preferences for the two separate steps, which have already been discussed in detail.
The invention relates also to novel compounds of formula V 
wherein, when n is 1,
R1 is naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, xcex2-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, each of which is unsubstituted or substituted by fluorine, hydroxy, C1-C18alkyl, C1-C18alkoxy, C1-C18alkylthio, di(C1-C4alkyl)amino, phenyl, benzyl, benzoyl or by benzoyloxy or R1 is a radical of formula II or III 
when n is 2,
R1 is phenylene or naphthylene each unsubstituted or substituted by C3-C4alkyl or by fluorine, or is xe2x80x94R6xe2x80x94Xxe2x80x94R7xe2x80x94,
R2, R3, Rxe2x80x24 and R5 are each independently of the others hydrogen, fluorine, hydroxy, C1-C25alkyl, C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted phenyl, unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; C1-C18alkoxy, C1-C18alkylthio, C1-C4alkylamino, di-(C1-C4alkyl)amino, C1-C25alkanoyloxy, C1-C25alkanoylamino; C3-C25alkanoyloxy interrupted by oxygen, sulfur or by 
xe2x80x83C6-C9cycloalkylcarbonyloxy, benzoyloxy or C1-C12alkyl-substituted benzoyloxy, or furthermore the radicals R2 and R3 or the radicals R3 and Rxe2x80x24 or the radicals Rxe2x80x24 and R5, together with the carbon atoms to which they are bonded, form a benzo ring, Rxe2x80x24 is additionally xe2x80x94(CH2)pxe2x80x94COR9 or xe2x80x94(CH2)qOH or, when R3 and R5 are hydrogen,
Rxe2x80x24 is additionally a radical of formula VI 
wherein R1 is as defined above for the case where n=1,
R6 and R7 are each independently of the other phenylene or naphthylene each unsubstituted or substituted by C1-C4alkyl,
R8 is C1-C8alkyl,
R9 is hydroxy,       [                  xe2x80x94O        -            ⁢              1        r            ⁢              M                  r          +                      ]    ,
xe2x80x83C1-C18alkoxy or 
R10 and R11 are each independently of the other hydrogen, CF3, C1-C12alkyl or phenyl, or R10 and R11, together with the carbon atom to which they are bonded, form a C5-C8cycloalkylidene ring unsubstituted or substituted by from 1 to 3 C1-C4alkyl groups;
R12 and R13 are each independently of the other hydrogen or C1-C18alkyl,
R14 is hydrogen or C1-C18alkyl,
R19, R20, R21, R22 and R23 are each independently of the others hydrogen, fluorine, hydroxy, C1-C25alkyl; C2-C25alkyl interrupted by oxygen, sulfur or by 
xe2x80x83C1-C25alkoxy; C2-C25alkoxy interrupted by oxygen, sulfur or by 
xe2x80x83C1-C25alkylthio, C7-C9phenyl-alkyl, C7-C9phenylalkoxy, unsubstituted or C1-C4alkyl-substituted phenyl; unsubstituted or C1-C4alkyl-substituted phenoxy; unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkoxy; di(C1-C4alkyl)amino, C1-C25-alkanoyl; C3-C25alkanoyl interrupted by oxygen, sulfur or by 
xe2x80x83C1-C25alkanoyloxy; C3-C25alkanoyloxy interrupted by oxygen, sulfur or by 
xe2x80x83C1-C25alkanoylamino, C6-C9cycloalkylcarbonyl, C6-C9cycloalkylcarbonyloxy, benzoyl or C1-C12alkyl-substituted benzoyl; benzoyloxy or C1-C12alkyl-substituted benzoyloxy; 
R24 is hydrogen, C1-C4alkyl, or unsubstituted or C1-C4alkyl-substituted phenyl,
R25 and R26 are hydrogen, C1-C4alkyl or phenyl, with the proviso that at least one of the radicals R25 and R26 is hydrogen,
R27 and R28 are each independently of the other hydrogen, C1-C4alkyl or phenyl,
R29 is hydrogen or C1-C4alkyl,
R30 is hydrogen, unsubstituted or C1-C4alkyl-substituted phenyl; C1-C25alkyl; C2-C25alkyl interrupted by oxygen, sulfur or by 
xe2x80x83C7-C9phenylalkyl unsubstituted or substituted on the phenyl radical by from 1 to 3 C1-C4alkyl groups; or C7-C25phenylalkyl interrupted by oxygen, sulfur or by 
xe2x80x83and unsubstituted or substituted on the phenyl radical by from 1 to 3 C1-C4alkyl groups,
R31 is hydrogen or C1-C4alkyl,
R32 is hydrogen, C1-C25alkanoyl; C3-C25alkanoyl interrupted by oxygen, sulfur or by 
xe2x80x83C2-C25alkanoyl substituted by a di(C1-C6alkyl) phosphonate group; C6-C9cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or C1-C12alkyl-substituted benzoyl; 
R33 is hydrogen or C1-C8alkyl,
R34 is a direct bond, C1-C18alkylene; C2-C18alkylene interrupted by oxygen, sulfur or by 
xe2x80x83C2-C20alkylidene, C7-C20phenylalkylidene, C5-C8cycloalkylene, C7-C8bicyclo-alkylene, unsubstituted or C1-C4alkyl-substituted phenylene, 
R35is hydroxy,       [                  xe2x80x94O        -            ⁢              1        r            ⁢              M                  r          +                      ]    ,
C1-C18alkoxy or 
R36 is oxygen, xe2x80x94NHxe2x80x94 or 
R37 is C1-C18alkyl or phenyl,
M is an r-valent metal cation,
X is a direct bond, oxygen, sulfur or xe2x80x94NR14xe2x80x94,
n is 1 or 2,
p is 0, 1 or 2,
q is 1, 2,3,4,5 or 6,
r is 1, 2 or 3, and
s is 0, 1 or 2,
with the proviso that when R2 and Rxe2x80x24 are hydrogen, methyl or tert-butyl or when R3 and Rxe2x80x24, together with the carbon atom to which they are bonded, form a benzo ring, at least one of the radicals R19, R20, R21, R22 and R23 is other than hydrogen and R1 is not unsubstituted naphthyl; with the proviso that R19 and R23 are other than hydroxy; and with the proviso that when R2 and Rxe2x80x24 are hydrogen, C1-C4alkyl or methoxy, R20, R21 and R22 are other than methoxy.
The preferred general symbols for the novel compounds of formula V correspond to those in the preferred general symbols set out hereinbefore for the process according to the invention for the preparation of compounds of formula I.